CN1081690A - Improved the polyolefine of barrier propterty - Google Patents
Improved the polyolefine of barrier propterty Download PDFInfo
- Publication number
- CN1081690A CN1081690A CN 93108113 CN93108113A CN1081690A CN 1081690 A CN1081690 A CN 1081690A CN 93108113 CN93108113 CN 93108113 CN 93108113 A CN93108113 A CN 93108113A CN 1081690 A CN1081690 A CN 1081690A
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- China
- Prior art keywords
- weight
- blend
- polymer
- polyolefine
- nitrile
- Prior art date
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Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 45
- 230000004888 barrier function Effects 0.000 title abstract description 7
- 239000011117 high nitrile polymer Substances 0.000 claims abstract description 29
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- 239000000203 mixture Substances 0.000 claims description 129
- 229920001903 high density polyethylene Polymers 0.000 claims description 54
- 239000004700 high-density polyethylene Substances 0.000 claims description 54
- 150000002825 nitriles Chemical class 0.000 claims description 46
- 239000000178 monomer Substances 0.000 claims description 29
- -1 polyethylene Polymers 0.000 claims description 26
- 229920001971 elastomer Polymers 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- 239000005060 rubber Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/18—Homopolymers or copolymers of nitriles
- C08L33/20—Homopolymers or copolymers of acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Disclosed the uniform polymer blend of outward appearance that improves barrier propterty, formed by 85-99.5% (weight) polyolefine and 15-0.5% (weight) high nitrile polymer.In addition, prepare container, have improved protective by 99.5-80% (weight) polyolefine and 20-0.5% (weight) high nitrile polymer.
Description
The present invention relates to the blend that high nitrile polymer (as vinyl cyanide-methyl acrylate copolymer) and various polyolefine generate, but the good characteristic of this blend condensation each component polymkeric substance or multipolymer is in one, thereby polyolefine is improved to protective, chemical resistant properties, intensity and the processing characteristics of solvent and gas.Nitrile polymer strengthens many polyolefinic barrier propterties greatly, and polyolefine is considered to infiltrative material.The rigid container that these blends are made comprises some large-scale products, as bucket and jar, film and moulded product, all shows the ability that restriction gas, steam and organic liquid penetrate, and is being applied aspect packing, thin-film material, automobile gasoline jar and the basin.And these blends provide the chance that adopts material cheaply and expensive polymkeric substance to make the product with advantageous property together.The present invention also provides the method that is generated blend by high nitrile polymer and polyolefine.
Because the major cause of polymer blending is a manufacturing matter good quality production economically, and polyolefinic cost low, be easy to get, so make aspect the type material very attractive.Polyolefine gains public acceptance because of the character that possesses many not ridges, for example, to the relative inert of water based product and many organic productss, even still has certain structure intensity and flexibility at low temperatures.In addition, polyolefine has the ability that limitation in height steam passes through, and therefore, they are applied in packaging industry.Polyolefine makes them can be used to make gasoline tank to the chemical resistant properties of organic solvent.Polyolefine should not be used for the place of strict protection gas.On the other hand, other polymkeric substance, as high nitrile polymer and multipolymer, its acrylonitrile content is outstanding organic steam and gas protection body up to more than 50%, has the character of the protection steam of outstanding anti-chemical and appropriateness.
Therefore, if comprehensively the advantageous property of each in these polymkeric substance is in one, that is just very favourable.High nitrile polymer and polyolefine combine and in fact are difficult for accomplishing, because their polarity dissmilarities are considered to inconsistent material.High nitrile polymer is chemical inert, because their character is polar, and polyolefine is nonpolar.Can give know they can not blend producing a kind of uniform component, and, under blending condition, can produce the system that highly is separated, the low interface interaction power between showing mutually and cause the transfer function of mechanical stress poor.
Known many patents provide the prescription of polymer blending, and wherein, a kind of component is a kind of graftomer, and it can contain a kind of alkene or elastoprene.Though contain alkene and vinyl cyanide in these prescriptions, they are general and can be used as independent polymer blending.
For example, United States Patent (USP) U.S.P.3634547 points out some graft copolymers, they are to be skeleton by the dience rubber multipolymer, by vinyl cyanide, vinyl ether, optionally aryl maleimide constitutes side chain, these graft copolymers can with the resin alloy that contains vinyl cyanide and unsaturated vinyl monomer, unsaturated vinyl monomer comprises alkene and optional N-aryl maleimide.Blend has high tensile strength and improved shock strength.
United States Patent (USP) 3652726 is similar to 3634547, has disclosed the blend of graft copolymer and copolymer resin.Graft copolymer contains the 1%N-aryl maleimide at least.Also contain a kind of aromatic olefin, as vinylbenzene.Copolymer resin comprises vinyl cyanide/aromatic olefin resin; Graft copolymer and various compatible resin are as the blend of ABS; Blend with vinyl cyanide, N-aryl maleimide, a kind of aromatic olefin and ABS graft copolymer.The character that these blends had can be with aforementioned patent comparable, also have high softening-point.
United States Patent (USP) 3962371 provides thermoplastic molding compounds, it is made up of the mixture of two kinds of parts, first component is vinyl cyanide, have a kind of aromatic ethenyl compound and the optional multipolymer of monoolefine at least, second component is the skeleton thing with the multipolymer of ethylene/vinyl base ester, and vinyl cyanide, vinyl aromatic compounds and optional monoolefine are the graft copolymer of grafting unit.
United States Patent (USP) 4397987 is pointed out anti-oily anti-ozone blend polymer, is made up of acrylonitrile/butadiene rubber and EPDM rubber, and the latter has the grafting branch of polymethylmethacrylate.
United States Patent (USP) 4409365 is pointed out the thermoplastic elastomer blend, is made up of two kinds of components.First component is the blend of crystalline polyolefin resin and sulfuration EPDM rubber, second component is the blend of crystalline polyolefin resin and sulfurized nitrile rubber, the latter comprises 1, the multipolymer of 3 divinyl formula isoprene and vinyl cyanide, the most handy one or more grafted functional group are carried out " functional group modification ", and such group comprises carboxyl and amino.This patent has also been introduced the paracril that utilizes toxilic acid modified polypropene and functional group modification in blend.
United States Patent (USP) 4588774 has disclosed another kind of thermoplastic compound's composition, and it is made up of methyl methacrylate, the maleimide of N-aryl replacement and a kind of terpolymer of vinyl aromatic monomers and the acrylonitrile copolymer that grafts on the polybutadiene rubber.
United States Patent (USP) 4605700 has been mentioned with the Article patent and similarly having been filled a prescription, and wherein the synthetic copolymer of the maleimide that replaces with alkene and N-aryl replaces terpolymer.
These patents have disclosed the blend that mixed with polymers generated, and one of them is an acrylonitrile polymer, and blend might not disclose the situation of the multipolymer that contains high acrylonitrile.The detailed description of relevant these polymkeric substance is seen the United States Patent (USP) 3426102,3586737 and 3763278 that has for its transferee.They are thermoplastic polymer basically, contain 70%(weight at least) unsaturated mononitrile, a kind of vinyl esters of unsaturated carboxylic acids and the rubbery copolymer that generates by conjugated diene and vinylbenzene or vinyl unsaturated nitrile.
The multipolymer of other thermoplastic polymer and these polymkeric substance has been described in seven pieces among the United States Patent (USP) that its transferee had.United States Patent (USP) 3914337 has disclosed the blend of high acrylonitrile multipolymer and vinyl cyanide and styrene resin smectic multipolymer.United States Patent (USP) 4153648 and 4195135 has disclosed the blend of high acrylonitrile multipolymer and vinyl cyanide indene copolymer.United States Patent (USP) 4160001 has disclosed the blend of high acrylonitrile multipolymer and methyl methacrylate and styrol copolymer.United States Patent (USP) 4307207 has disclosed the blend of high acrylonitrile content multipolymer and hydrophobic nylon.United States Patent (USP) 500483 has proposed the blend of the thermoplastic polymer of high nitrile multipolymers and polar functionalities.United States Patent (USP) 4914138 has proposed the polyolefinic blend of high nitrile polymer and functional group modification.United States Patent (USP) 5084352 proposes the multilayer proofing structure, and wherein, one deck is a kind of multiphase polymer high-nitrile blend, and it can comprise high nitrile multipolymers and a kind of polyolefine.Last piece United States Patent (USP) 4123576 has disclosed the multilayer proofing structure, and wherein, one deck is that polymer blend is made, by 20%(weight at least) lonitrile copolymer and 80%(weight at least) polyolefine formed.
Blend of nylon demonstrates improved shock-resistance, can be used for kind of a thermoformed articles.Other blend has improved gas proofness and other mechanical properties makes them suitable to wrapping material.Though existing many blends that relate to acrylonitrile polymer and other polymkeric substance,, above-mentioned patent is not mentioned by the high acrylonitrile polymkeric substance and is not contained the polyolefinic blend of functional group, and this blend is that outward appearance is uniform composition.
The purpose of this invention is to provide compatible polymer blend, its mechanical properties and chemical property are improved.
Another object of the present invention provides compatible polymer blend, and its polymeric components cost is low, and processing characteristics is improved.
Further object of the present invention provides the compatible polymer blend that can be used for producing film, barrier film and rigid container, the perviousness of gas, steam and organic liquid is provided constraints.
A further object of the invention provides the method for preparing high cyanogen polymkeric substance and polyolefinic blend.
Summary the present invention all purposes provide the product that surpasses known polymer blend advantage, can well be confirmed from the description of following specification sheets.
Usually, polymer blend of the present invention comprises about 0.5-15%(weight) high nitrile polymer, better be 1-12%(weight), 3-10%(weight preferably).But generate high nitrile polymer by the mono-vinyl monomer polymerization of single unsaturated nitrile of major part and small portion copolymerization, reaction also can be carried out in the presence of dience rubber.Also comprise 85-99.5%(weight) polyolefine.Better be 88-99%(weight), 90-97%(weight preferably).Term of the present invention " polyolefine " broadly refers to any hydro carbons thermoplastic polymer that can be made by alkene, as polyethylene (LLDPE, LDPE, HDPE etc.), polypropylene, polybutene, polypenthylene, its multipolymer or blend, do not comprise that any functional group modification is to improve the polyolefine (seeing United States Patent (USP) 4914138) with the nitrile consistency.
The present invention further provides container, the most handy blowing mould formula injection molding by above-mentioned polymer blend preparation.The raw material of preparation container consists of 0.5-20%(weight) high nitrile polymer and 80-99.5%(weight) polyethylene.
The present invention also provides a kind of polymer blend, and it is by 0.5-30%(weight) high nitrile polymer, 70-99.5%(weight) polyolefine and a kind of expanding material composition.But the former is formed by the mono-vinyl monomer polymerization of single unsaturated nitrile of major part and small portion copolymerization.Polymer blend consists of 1-25%(weight preferably) high nitrile polymer and 75-99%(weight) polyolefine.Be preferably 3-20%(weight) high nitrile polymer and 80-97%(weight) polyolefine.
Polymer blend of the present invention is made up of two or more polymkeric substance.A kind of is high nitrile polymer, be meant nitrile polymer in polymkeric substance greater than 50%(weight), another kind is a polyolefine, will be discussed herein.
Specifically, nitrile polymer of the present invention be by the single unsaturated nitrile (for example vinyl cyanide) of major part but and the mono-vinyl monomer polymerization of small portion copolymerization and generating, reaction can be carried out in the presence of dience rubber.But the homopolymer of dience rubber conjugate diene monomer or multipolymer.
High nitrile polymer of the present invention can comprise mass polymerization, solution polymerization and the suspension polymerization of letex polymerization formula with any known polymerization technique preparation, and the adding of monomer and other component can be taked in batches, continuous or mode intermittently.Recommend emulsion or suspension polymerization, in aqueous medium, in the presence of free-radical initiator, temperature is 0 °-100 ℃, and essentially no molecular oxygen exists.
Alkene unsaturated nitrile of the present invention is α, the unsaturated mononitrile of β-alkene, and structural formula is:
Wherein, R is H, C
1-C
4Low alkyl hydrocarbon or halogen.Such compound comprises vinyl cyanide, α-Lv Bingxijing, α-fluorine vinyl cyanide, methacrylonitrile, ethyl acrylonitrile etc.The used unsaturated mononitrile of alkene of the present invention is vinyl cyanide, methacrylonitrile and composition thereof most preferably.
Can comprise one or more alkene esters of unsaturated carboxylic acids, vinyl ester, vinyl ether, vinyl ketone, alpha-olefin, vinyl aromatic monomers etc. with alkene unsaturated nitrile polymer monomers component.
The alkene esters of unsaturated carboxylic acids has structural formula:
Wherein, R
1Be H, C
1-C
6Alkyl or halogen.R
2Be C
1-C
30Alkyl.This compounds comprises methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate and vinylformic acid pentyl ester, Ethyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, α-Lv Bingxisuanjiazhi, α-Lv Bingxisuan ethyl ester etc.Most preferably methyl acrylate, ethyl propenoate, methyl methacrylate and Jia Jibingxisuanyizhi.
Alpha-olefin of the present invention is C
4-C
10Alkene, structural formula is:
Wherein, R
3And R
4Be C
1-C
7Alkyl, they are iso-butylene, 2-methyl butene-1,2-methylpentene-1,2-methyl hexene-1,2-methyl heptene-1,2-methyl octene-1,2-ethyl butene-1,2-propyl group butene-1,2 specifically, 4,4-2,4,4-Trimethyl-1-pentene-1 grade and their mixture, most preferably iso-butylene.
Vinyl ester comprises methyl ethylene ester, cyclic olefin copolymers, ethylvinyl, propyl ethylene base ester and butyl vinyl ester, isopropyl methyl ester, ethyl isopropyl esters etc.Most preferable vinyl ester, cyclic olefin copolymers, ethylvinyl, propyl ethylene base ester and butyl vinyl ester.
Vinyl ester comprises vinylacetate, vinyl propionic ester, vinyl butyrate etc.Vinylacetate most preferably.Vinyl aromatic monomers comprises vinylbenzene, alpha-methyl styrene, Vinyl toluene, vinyl-dimethyl benzene and indenes etc.Vinylbenzene most preferably.
Olefin nitrile copolymer can be chosen under the existence of moulding dience rubber and carry out polymerization, and dience rubber can be the homopolymer or the multipolymer of conjugated diene monomer.Diolefinic monomer comprises 1,3-butadiene, isoprene, chloroprene, bromine divinyl, cyano group divinyl, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene etc.Most preferably 1,3-butadiene and isoprene, the two be easy to get and polymerization good.
Conjugate diene monomer can with comonomer generation copolymerization, the latter can be selected from vinyl aromatic monomers, following formula vinyl nitrile monomer:
(wherein, the R name is the same) and following formula ester monomer:
(wherein, R
1And R
2Name is the same).Rubbery polymer contains 50-100%(weight) polymerized conjugated diene base monomer and 0-50%(weight) comonomer.
The preferred polymkeric substance of the present invention is that (A), (B), (C) the three component polymerizations of 100 parts (weight) make by total amount.Wherein, (A) 50-90% contains a kind of following formula nitrile monomer at least.
Wherein, the R name is the same.(B) be (A) and (B) the 10-40%(weight of gross weight), be selected from following formula ester monomer.
(wherein, R
1And R
2Name is the same), the following formula alpha-olefin:
(wherein, R
3And R
4Name is the same), be selected from vinyl ether, vinylacetate, vinylbenzene and the indenes of methylvinylether, ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether.(C) rubbery polymer of 0-40 part conjugated diene monomer can be selected divinyl and isoprene for use, the optional vinylbenzene of comonomer, following formula nitrile monomer.
(wherein, the R name is the same) and following formula ester:
(wherein, R
1And R
2Name is the same).This rubbery polymer contains polymeric conjugated diene 50-100%(weight), comonomer 0-50%(weight).The preparation of most preferred nitrile polymer is by (A) 70-80 part (weight), (B) 20-30 part (weight) and (C) 5-15 part (weight) polymerization obtain.Shi Yi nitrile polymer is Barex especially
210 resins, the trade name of the Industrial products of BP America Inc., it be poly-(vinyl cyanide-methyl acrylate-divinyl) (70-21-9), number-average molecular weight is 50000.
By 70%(weight at least) single unsaturated nitrile and 30%(weight) a kind of comonomer, the latter can be a modified rubber, and the thermoplasticity high nitrile resin of being formed is at United States Patent (USP) 3426102,3586737,3763278 are described, and the main contents of the document are incorporated herein by reference.These polymkeric substance have outstanding barrier propterty, can make container, tubing, film and sheet material etc. by molding, are used to pack various types of solids, liquids and gases.
As described in United States Patent (USP) 4914138, because the phase separation of height, high nitrile polymer and polyolefinic blend are considered to inconsistent usually.For the component that has such low-affinity each other, melt interface tension force height is difficult to the dispersion mutually that reaches meticulous.The terms of settlement of 4914138 pairs of inconsistent problems of United States Patent (USP) is with the polyolefine functionalization that has polar group, makes it compatible with high nitrile polymer.In more detail, the functional group that is inserted on the molecular polyolefin chain makes the reflecting point on the high nitrile polymer molecular chain produce intermolecular interaction from molecular level, and these interactions are considered to the compatible reason of blend component.The present invention proposes to utilize the hydro carbons polyolefine of non-modified to improve the consistency of high nitrile component in they and the mixture.Have found that directly making polyolefine and the rubber polymer blend that contains nitrile is possible to produce the uniform composition of outward appearance.In the blend of the rubber polymer of polyolefine and grafting nitrile, add expanding material and can further increase the amount that is combined in the nitrile polymer in the blend, obtain anti-chemical and protective improved products.
The used suitable polyolefine of the present invention is by C
1-C
6The polymkeric substance that α-monoolefine makes, representative is polythene PE, the copolymer p EP of polypropylene PP and ethene and propylene.
What value row was noted is, exists even there is compatibilizing agent, and processing conditions and physical compatibility that the rheological characteristics of two kinds of components, polyolefine and high nitrile resin blend are adopted also all can reach requirement, and key depends on the concentration of nitrile polymer component.Under according to the determined processing conditions preferably of two component character, even when no compatibilizing agent, can also obtain the uniform composition of the improved outward appearance of mechanical properties, barrier propterty and chemical resistance.Available conventional extrusion equipment reaches maximum mixing, compares with polyolefine, and the fusing point of these blends is more lower slightly.Must avoid in extrusion screw, producing the high pressure area so that nitrile polymer and polyolefinic consistency variation cause that mixed effect reduces.Do not produce the standard mixing device of high pressure area, as hybrid ring, deuterostrophies sheet, Maddox type mixing section etc. can produce the uniform blend of ideal outward appearance.Yet, when reverse trend appears in the improvement of mechanical properties, during the boundary of the 10-15% that the concentration of high nitrile resin has reached, at this moment, add compatibilizing agent and just become important, can produce than the low heterogeneous materials of single polyolefine component melt viscosity.Also observe, at content up to 15% high nitrile polymer (Barex
210 resins, the assignee of the present invention produces) blend processing during, they have melt strength preferably, so reduced the tendency of this blend sagging in extrusion-blown modling is processed, the contraction when also having reduced from mould outlet.
These blend product can comprise extrusion-blown modling, film blowing and injection blow molding engineering and industrial being applied because of its some performance.The influence of the low levels high nitrile polymer that the melting temperature is existed, they can be used as polyolefinic processing aid.Such melt characteristic is very important in rotational molding and injection-molded such specific area.Actually operating during strong revolving die is moulded is anti-chemical and a rigidity of utilizing the improvement product of crosslinked HDPE and LLDPE.We find that the present invention adopts the blend of novel HDPE/ high nitrile polymer, and above-mentioned performance is improved.The main drawback that utilizes crosslinked class polyolefin is the cost problem, and for example, HDPE rotational molding level is 0.60 dollar/pound, and crosslinked level is 1.20 dollars/pound.Other shortcoming is must take measures to avoid in the storage period before loading, storage and sex change because of overheated premature setting.The thermostability of low melting characteristic that the high nitrile blend of HDPE/ of the present invention is had and height makes them become the only material of preparation bucket and tun (25 add storehouse-20000 adds the storehouse).Another advantage of using this technology is to utilize than being used in the high HDPE of molecular weight in the rotation mold usually, and the character of roational molding product is improved.
By adding suitable compatibilizing agent, the character of polyolefin resin blend of the present invention can be improved.It should be noted that only needs very a spot of compatibilizing agent, depends on that product reaches optimum performance, and its consumption can hang down and reach 0.1%(weight), up to 5%(weight), better be 0.1-4%(weight), 0.1-3%(weight preferably).
Have found that, the blend of polyolefine/high nitrile polymer of the present invention, the alternating copolymer of alpha-olefin and maleic anhydride (MA) can play the function of compatibilizing agent very effectively.
The present invention can also utilize paucidisperse agent/softening agent (as calcium stearate or Zinic stearas) to improve mechanical property, the appearance surfaces character of for example fall bottle shock strength and product.
Especially exemplified by following examples to further describe the present invention.
Embodiment 1
With Brabender instrument (Brabender) preparation 95/5HPDE/Barex
210 blends
In a torque rheometer (C.W.Brabender, PLD-331 type), mix 47.5 gram high density polyethylene(HDPE)s (Dow grade 62013) and 2.5 gram Barex
The 210(extrusion grade), deciding speed of rotation is 35 rev/mins, 200 ℃ of initial temperatures, and mixture stirred 5-10 minute.
Embodiment 2
Obtain 95/5HPDE/Barex with the Brabender instrument
210 blends prepare film
The blend preparation is as example 1.From the Bu Shi instrument, took out 95/5 HDPE/Barex in last 5 minutes rapidly
210 blends (approximately need 30 seconds to 1 minute) are transferred to giving in the thermal model of the Wabash rolling press that gives heat immediately, at 200 pounds/square inch and 200 ℃ of dip molds, cool off 10-12 minute preparation flat board of rolling press (3 " * 6 " * 1/8 ") under applied pressure.Flat board is cut into 1 square inch of size with band saw.95/5HDPE/Barex
The preparation of 210 films is by the platelet 1 square inch of two ends, the end, pressuring template top pressing mold, with the cutting of EKCO Baker ' s Secret pastry slicer (metallic surface scribbles the silicon compound of non-toxicity FDA approval).Working conditions is 1000 pounds/square inch (0.69 crust), 200 ℃ 1 minute.About 7 mils of film thickness (177.8 microns).
Embodiment 3
The HDPE and the Barex that add compatibilizing agent with the preparation of Brabender instrument
210 blends.
The blend preparation is as precedent.Granular HDPE, i.e. the product 62013(48.375 of Dow company gram) and 1.25 gram Barex
The 210(extrusion grade) and the multipolymer of 0.375 gram octadecyl and maleic anhydride mix mutually.The latter is free-pouring white powder, and fusing point is 120-131 ℃.Sell by Chevron chemical company (Chevron Chemical Co.).Trade name PA-18.Other step is similar to precedent.
Embodiment 4
Add and do not add compatibilizing agent and produce HDPE and Barex
The granular blend of resin.
HDPE and Barex
The sample of resin binary and ternary blends carries out granulation with the Prodex single screw extrusion machine before blowing.The extruder screw diameter is 1.75 inches, compression ratio 2.0: 1, and the forcing machine length-to-diameter ratio is 26: 1.Screw-rod structure comprises heating zone, zone of transition and metering zone.Before component directly entered forcing machine, a Conair Mircroconomix volume kneading machine was used for keeping component to obtain good blend.Five heating zone of all of forcing machine garden tube all maintain 390 °F (198.9 ℃).Screw speed is 60 rev/mins, and the melt temperature of extrudate is 400 °F (204 ℃).To all blends, it is certain that all processing conditionss keep.
Classical group with this method preparation becomes to see Table 1.
Table 1
HDD/BAREX
The preparation of blend
Sequence number Barex
210 resin compatibilizing agent (Actonel) Zinic stearass
(% weight) % (weight)-active (% (weight)
1 3.5 0 0
2 5 0 0
3 10 0 0
4 15 0 0
5 10 1 0
6 15 3 0
7 15 3 0.1
All these components have produced the uniform blend of outward appearance.Typical blend and HDPE(Paxon BA 50-100) rheological characteristics see Table 2.
Table 2
HDPE/BAREX
The rheological characteristics of blend
Resin/blend viscosity, second
-1Viscosity, 1000 seconds
-1Shearing sensibility
(thousand pools) (thousand pools) (1/1000)
HDPE 281.0 4.80 58.5
95/5 128.6 4.42 29.1
HDPE/Barex
Resin
90/10 97.5 3.89 25.1
HDPE/Barex
Resin
Embodiment 5
From HDPE/Barex
Resin blend prepares rigid container
Extrude bottle blowing machine (BM04 type) with single mode hole Bekum formula and make blend be configured as one pint rigid container, the blending resin of employing is HDPE(Paxon BA 50-100)/Barex
This screw rod working speed is 15 rev/mins, and compression ratio is 2.5: 1, is equipped with the Maddox mixing head, and blow gas pressure is 80 pounds/square inch.The temperature distribution situation is, is 320 °F at feeding part, and metering end is 390 °F.About 28.5 grams of rigid container.
Observed typical extrusion characteristics sees Table 3.
Table 3
HDPE/BAREX
The extrusion-blown modling of resin blend
Form extrudate fusing point head pressure penetrating velocity
HDPE/Barex
210 pound/inches
2Grams Per Minute
Resin
100/0 393 1590 106
95/5 402 1250 112
90/10 387 1110 111
84/15 395 980 113
Embodiment 6
Use HDPE/Barex
Resin blend is to change in the mold and is shaped
Contain 10%Barex
The HDPE(Paxon BA50-100 of 210 resins)/Barex
The granular blend of 210 resins is ground into less than 35 purpose powder under 140 °F (60 ℃) in the pin type shredder.Powder is packed in changeing mold, place stove, rotated 15 minutes down at 550 °F.After the cooling, from mold, remove solid shaping thing.Comparing test is to adopt the HDPE powder similarly to test under identical condition separately, and the object that is produced is not fused, loose bonded powder.
Test of products
By the Brabender instrument or extrude the binary blend that instrument generates and the ternary blends that adds compatibilizing agent make film by pressing mold chemical resistant properties test
Test binary or ternary (adding compatibilizing agent) blend pressing mold are made the anti-chemical of film.Film is fixed to the transmission of glass steam penetrates on the bottle, with reference to ASTM method D-814-86, bottle is (236 centimetres of 1/2 pints
3) the Mason bottle, be equipped with metal ring Kerr nut and additional smooth edge, flat.Nut and ring make the edge of sample against bottle, and the diameter that exposes the garden area of each sample of doing test is 2.188 inches (55.5 millimeters).
About 200 milliliters of dimethylbenzene of packing in each bottle with electronic digit device to test thickness of sample, are accurate to 0.001 inch.Write down the bottle initial weight of pack into solvent and test film, be accurate to 0.005 gram.Careful sealing bottle, and at room temperature put into a draughty stove.Bottle keeps the vertical position, not directly contact between solvent and the test sample.Test is at room temperature carried out, and writes down per 24 hours weightlessness, 15-30 days at least.Each sample will prepare two, and their composition is identical.Rate of permeation is to get from two resulting mean values of assay flask.
By the Brabender instrument or extrude the chemical resistant properties that binary blend (not adding mutual solvent) that instrument generates and ternary blends (adding compatibilizing agent) make film by pressing mold and see Table 4-7.
Table 4
The chemical-resistant of polyolefine/Barex 210 Brabender blends improves
Sequence number Barex
The anti-chemical of 210% (weight) is improved (%)
1 2.5 7.9
2 20.0 21.1
Test sample is the pressing mold film.
Table 5
HDPE/Barex
210 extrude the improvement of the anti-chemical of blend
Sequence number Barex
210 anti-chemical are improved
% (weight) (%)
1 1.5 6.9
2 2.5 26.1
3 5.0 29.0
Test sample is the pressing mold film.
The used compatibilizing agent of some sample is expressed as follows: BM-30 is the terpolymer of iso-butylene (IB), maleic anhydride (MAH) and N-phenylmaleimide (PMI), three's mole ratio is 0.5: 0.35: 0.15, molecular weight is 30000, softening temperature 150-160 ℃, sell by Kuraray company limited.
PA-18 is the multipolymer of octadecyl and maleic anhydride, is a kind of alternating copolymer, and as previously mentioned, it can have been bought from Chevron chemical company.
PMVE-MA is the multipolymer of vinyl methyl ether and maleic anhydride, is sold by GAF company.
Table 6 confirms that with three kinds of different compatibilizing agents to the nitrile polymer of same amount, the increase of their amounts does not cause that the anti-chemical of these blends has more improvement, sees example 1 and 2,3 and 4,11 and 12,13 and 14,18 and 19,20 and 21.
Table 6
(be added with the Brabender blend HDPE/Barex of compatibilizing agent
210 chemical-resistants improve
Barex
210 compatibilizing agents
1Chemical resistant properties is improved (%)
The type of sequence number (% weight) (%, weight) compatibilizing agent
1 5 2.5 BM-30 10.7
2 5 5.0 BM-30 5.9
3 12.5 2.5 BM-30 23.2
4 12.5 5.0 BM-30 25.1
5 20.0 2.5 BM-30 10.0
6 20.0 5.0 BM-30 27.4
7 2.5 0.375 PA-18 12.5
8 2.5 0.75 PA-18 30.3
9 5.0 0.75 PA-18 10.0
10 5.0 1.5 PA-18 21.5
11 12.5 0.75 PA-18 22.3
12 12.5 1.5 PA-18 21.3
13 20.0 0.75 PA-18 29.9
14 20.0 1.5 PA-18 28.0
15 2.5 0.75 PMVE-MA 8.4
16 2.5 1.5 PMVE-MA 39.5
17 5.0 0.75 PMVE-MA 17.1
18 5.0 1.5 PMVE-MA 22.8
19 5.0 3.0 PMVE-MA 20.3
20 12.5 1.5 PMVE-MA 23.6
21 12.5 3.0 PMVE-MA 20.9
The ratio of relevant best nitrile/compatibilizing agent, the blend that adds compatibilizing agent that can observe in the forcing machine preparation has identical trend with the blend that makes at the Brabender instrument.For relatively, see also example 1,2,3 and 4 and example 5 and 6(table 7).
Table 7
What add compatibilizing agent extrudes blend HDPE/Barex
210 chemical-resistant improves
Barex
210 chemical resistant propertiess are improved (%)
Sequence number (% the weight) (type of compatibilizing agent (%, weight) compatibilizing agent
1 1.5 0.375 PMVE-MA 5.7
2 2.5 0.375 ″ 25.1
3 2.5 0.75 ″ 19.6
4 2.5 1.5 ″ 27.3
5 5.0 1.5 ″ 29.6
6 10.0 1.5 ″ 44.7
7 10.0 1.5 ″ 43.3
8 1.5 0.75 ″ 24.9
9 2.5 0.375 ″ 30.8
10 2.5 0.75 ″ 46.3
11 3.5 0.75 ″ 19.6
12 5.0 0.75 ″ 35.3
13 10.0 0.75 ″ 31.4
With Bekum BM04 machine HDPE/B210 binary blend and the ternary blends that adds compatibilizing agent are carried out the blowing mould test
Testing sequence
Bekum BM04 with 60 mm dias extrudes the blow molding machine bottle blowing.HDPE, Barex
210 and/or the binary of compatibilizing agent and ternary blends pack into and extrude bottle blowing machine, charging can be to give making granulous or exsiccant blend.The feeding temperature of forcing machine schedules 320 °F to avoid too early fusing, and blow gas pressure maintains 80 pounds/square inch.With length-to-diameter ratio is several screw rods of 24: 1, and compression ratio is 1.8-3.0.With having compression ratio is 2.5: 1 routine processing screw rod bottle blowing.Typical situation is that a kind of blend blows out 100-300 bottle and tests.At whole on period, head and melt temperature, polymer melt pressure and bottle are heavy to be monitored and record always.
Contain 5% and 10%Barex
The evaluation test of some blowing mould condition of 210 binary blend sees Table 8.
Table 8
Extrude the blowing mould evaluation
With the variation of processing and composition, the reduction of blend rate of permeation
The melt temperature chemical resistant properties is improved %
(℃)
200 20.4
220 24.2
Screw design
Screw rod A 22.2
Compression ratio 3:1
Screw rod C 22.4
1.82 compression ratio
Weight control
The sedimentation forcing machine
11 25.8
16 18.9
Barex concentration %
5 18.9
10 25.8
From HDPE and Barex
The granular blend of 210 resins and dry granular blend prepare blow molded bottle permeability data relatively see Table 9 and 10.
Table 9
HDPE/Barex
The dimethylbenzene permeability reduction of 210 binary blend
(blow molded bottle that makes from granulated product)
Sequence number Barex
210 permeability reductions (%) blend type
% (weight)
1 5.0 0.0 dry blends
2 10.0 4.0 dry blends
3 15.0 10.0 dry blends
* test sample: bottle wall % (weight)
Solvent: dimethylbenzene
Test temperature: 40 ℃
Table 10
HDPE、Barex
210
The permeability reduction of the blowing mould bottle that blend and OCTD-co-MA make as the dry blends of compatibilizing agent
Sequence number Barex 210 compatibilizing agents (% weight) permeability reduction
(% weight) is (%) (Actonel)
1 13 1 26.2
2 15 3 28.6
3 19 3 40.8
* test sample: bottle wall
Solvent: dimethylbenzene
Test temperature: 40 ℃
HDPE/Barex
The reduction of the oxygen transmission speed (OTR) of 210 resin blends and similarly relatively see Table 11 through 4 grades of containers of fluorine sealing.
Table 11
HDPE/BAREX
The antioxygen of 210 resin blends
Sample is formed the OTR cubic centimetre, and (the standard temperature is than the improved % of contrast
High nitrile resin %, weight degree and pressure)/day/
Standard atmospheric pressure
Contrast
4 Barex
210E 2.13 8.2
Resin (colour-stable)
5 Barex 210E?PHW 1.83 22.0
Resin (colour-stable)
5Barex
210E resin 2.18 6.0
6Barex
210E resin 1.81 22.0
5Barex
210I resin 2.02 13.0
5Barex
218 resins 1.92 18.0
10Barex
The 210E resin
a1.52 39.4
Fluorochemical HDPE container-4 grade
b2.13 15.1
A) with 1%Actone 1 increase-volume, contain 0.01% Zinic stearas.
B) internal surface and the outside surface of the close 4 grades of bottles of fluorine
Annotate: the antioxygen test of 12 oz containers is that with the test of storehouse, storehouse overall package oxygen dialysis instrument, experiment repeats secondary under 73 and wet condition.
HDPE/Barex
Resin blend is made the dimethylbenzene of bottle and the test of dimethylbenzene/methanol permeation character
Whole bottle is used in these tests.In bottle, add dimethylbenzene, methyl alcohol or dimethylbenzene/carbinol mixture that about 200 millis are opened.Bottle aluminum slice heat seal, bottleneck is tight with nut cap.Assay flask is weighed and is accurate to 0.005 gram, is positioned in the draughty stove, and temperature is 140 °F, and the weightless situation of per 24 hour records continues 15-30 days at least.At last, air-tight bottle allows at room temperature to place 24 hours, and also " evaluation " observation is to determine any sign of sealing leak, and finding has the bottle of leakage promptly to abandon it.
Utilize extensive stock level Barex
The typical testing permeability that the serial HDPE/Barex resin blend that 210 resins are generated is made bottle the results are shown in Table 12.
Table 12
HDPE(Paxon BA50-100)/BAREX
Resin
The penetration property of blend
(the improvement percentage ratio that surpasses the HDPE comparative sample)
Sample survey dimethyl phenyl carbinol dimethylbenzene/methyl alcohol
% (weight) mixture
/ high nitrile/resin
4 Barex
210E 7.6 72.7 0.0
Colour-stable resin
5 Barex
210E 13.7 77.2 12.3
Colour-stable resin
5 Barex
210E 4.0 54.5 4.3
Colour-stable resin
6 Barex
210E 12.1 36.3 12.9
Resin
5 Barex
210I 7.1 77.2 7.4
Resin
5 Barex
218 7.6 77.2 8.0
Resin
7.5Barex
218 11.7 77.2 12.9
Resin
The test of the post crushing strength of whole bottle
Blowing mould bottle (1 pint) is 0.30 inch with pinblock speed
2/ minute compression testing machine test.Bottle is placed in the free activity of an eck and does not run in the drill jig of pinblock, carries out inverted running, has measured stress-strain curve thus, and the representative data that his-and-hers watches 13 propose calculates.
Table 13
By HDPE/BAREX
The post crushing strength of the rigid container of 210 resin blends preparation
Barex
210 resins 05 10
a15
a
% (weight)
Bottle weighs 27.7 29.9 31.5 33.0
Gram
Sidewall thickness 27.0 33.0 35.0 33.0
Millimeter
Maximum load pound 104.9 152.4 183.3 222.0
Rigidity, pound/40,903 53,145 62,260 69449
Total energy 41.2 51.2 54.1 80.1
In-lb
Modulus of elasticity, 6,286 9,561 9,561 10665
Pound/square inch
A) with 3%Actone 1 increase-volume
The test of environmental stress crack resistance
Each assay flask is packed the 10%Igepal solution of capacity into at the bottom of flooding bottle.Seven bottles wherein are installed on the pressure line that keeps 15 pounds/square inch, keep 30 days down at 100 °F.In case bottle breaks, test is interrupted, the record disruptive time.Test latter stage, each bottle carries out pressure test and guarantees leakless, and test-results sees Table 14.
Table 14
The cracking of the anti-environmental stress of resin blend
140 °F, 5 pounds/inch
2Level pressure, 10%Igepal25% bottling amount,
15 day trial period, 7 samples
Form stress rupture and count note
Comparison (HDPE paxon BA 50-100) 3
5% Barex
210E resin 0 extrusion die level
6% Barex
210E resin 0
10% Barex
210E resin 0 2% Actone+0.10%
Zinic stearas
4% Barex
210E resin 0
(colour-stable)
5% Barex
210E resin 0
(colour-stable)
5% Barex
210I resin 0 injection mould level
High-grade rubber
5% Barex
218 resins 1
7.5% Barex
218 resins 0
Fluoridize (HDPE) 3 for 4 grades
Embodiment 10
Measure the variation of the polymer morphology of HDPE/Barex210 blend
Dispersion agent/softening agent (Zinic stearas) is promoted HDPE phase and Barex
The influence of the adhesive attraction between 210 phases can be arrived by electron microscope observation.By HDPE, Barex
The blend that 210 resins and a kind of compatibilizing agent (ACTONE 1) are formed and contain HDPE, Barex
The improvement situation of the anti-dimethylbenzene of the system of 210 resins, compatibilizing agent (ACTONE 1) and dispersion agent (0.1% Zinic stearas) relatively see Table 15.
Table 15
HDPE/BAREX
The morphology of 210 resin blends
Sample survey, % (weight) is in dimethylbenzene
HDPE/Barex
210 rate of permeation are improved
Resin/ACTONE 1/ Zinic stearas morphology is described %
The anti-dimethylbenzene of 84/15/1/0 extended district 13
82/15/3/0 extended and laminar region 4
Insufficient adhesion
81.9/15/3/0.1 extended and laminar region 40
The good interface adhesion phenomenon
High density polyethylene(HDPE) is compared with the competitive material of nitrile polymer blend and other, and one of its advantage is that cost is low.Another important aspect of the present invention is its multifunctionality.Polyolefine is because of its different molecular weight, polymolecularity, the degree of branching, comonomer, flow characteristics and show different density and degree of crystallinity, so can obtain many different grades.The polyolefine of any grade can with the nitrile polymer combination.Must and need improved special property to be selected according to type used.
The availability of the nitrile polymer of different grades and different melt flow characteristics also is equal important, selects grade hard or softer can make nitrile polymer be used to make sheet material and bottle.Another advantage of the present invention comes from the character of nitrile polymer, can select many different working methods, comprises that sheet material extruding, thermoforming, extrusion-blown modling, blown film are extruded and pipe is extruded.
Nitrile polymer such as Barex
210 extrusion grades, Barex
210 injection grade and HI high impact level Barex
218 resins, their blend can be used for regulating the flow characteristics of nitrile component to obtain desired machined parameters.In turn, nitrile polymer as the block polymer of vinyl cyanide and methyl acrylate and/or the block polymer of vinyl cyanide and methacrylonitrile, when not containing rubber component, can use separately or and Barex
210 and/or the Barex218 resin alloy, when main purpose is that they can be used as the protection component in the blend when improving chemical resistant properties.When needing the addition character of polyolefine/nitrile blend,, can use the same method as processing characteristics, mechanical property, chemical resistant properties, gas shield.It is lower that importance of the present invention obtains the employed processing temperature of these blends, makes the blend of preparation have character preferably, prevents the degraded of each component and saves energy.Have to be noted that the blend of describing is regeneration and reusable alternative here.
The present invention relates to generate the polymer blend that outward appearance is uniform, be used for the chemistry/gas packing.The important key parameter that control generates the uniform polyolefine of outward appearance/nitrile blend and improved mechanical properties and improved flow characteristics is flow characteristics, the type of compatibilizing agent (as needs) and the synergistic effect of amount and compatibilizing agent/dispersion agent of molecular weight and two components.Based on these effects, the present invention has shown that the concentration of protection component and compatibilizing agent can reduce, and the economy that can obtain.
Claims (9)
1, a kind of container, form by a kind of polymer blend:
(A) 0.5-20% (weight) high nitrile polymer, but form by the mono-vinyl monomer polymerization of single unsaturated nitrile of major part and small portion copolymerization;
(B) polyolefine of 80-99.5% (weight).
2, container according to claim 1 is by 1-15%(weight) high nitrile polymer and 85-99%(weight) polyolefine makes.
3, container according to claim 2 is by 3-10%(weight) high nitrile polymer and 90-97%(weight) polyolefine makes.
4, container according to claim 1, wherein, polyolefine is C
2-C
6α-monoolefine.
5, container according to claim 1, wherein, polyolefine is a polyethylene, polypropylene, polybutene, polypenthylene, at least two kinds of monomeric multipolymers in ethene, propylene, butylene or the amylene, or its blend.
6, according to the container of claim 5, wherein, polyolefine is a polyethylene, and it is selected from linear low density polyethylene (LLDP), new LDPE (film grade) (LDPE) and high density polyethylene(HDPE) (HDPE);
7, according to the container of claim 1, wherein, high nitrile polymer is can be polymerized in the presence of dience rubber with the mono-vinyl monomer of nitrile copolymerization by single unsaturated nitrile of major part and small portion.
8, according to the container of claim 10, wherein, high nitrile polymer (A) with (B) by being polymerized, wherein:
(A) be α, β-thiazolinyl saturable mononitrile, structural formula is:
Wherein, R is H, C
1-C
4Alkyl or halogen than low-carbon (LC);
(B) be can with a kind of monomer of α, the unsaturated mononitrile copolymerization of β-thiazolinyl, be selected from thiazolinyl esters of unsaturated carboxylic acids, vinyl ester, vinyl ether, vinyl ketone, alpha-olefin, vinyl aromatic monomers and their mixture;
9, container according to claim 1, wherein, high nitrile polymer by total amount be 100 parts (weight) (A) and (B) the component polymerization generate.
(A) 50-90%(weight), contain a kind of α, the unsaturated mononitrile of β-thiazolinyl at least, its structural formula is:
Wherein, R is H, C
1-C
4Alkyl or halogen;
(B) monomer 10-15%(weight) is selected from:
(ⅰ) following formula ester:
Wherein, R
1Be H, C
1-C
6Alkyl or halogen;
R
2Be C
1-C
30Alkyl;
(ⅱ) following formula alpha-olefin:
Wherein, R
3And R
4Be C
1-C
7Alkyl,
(ⅲ) vinyl ether is selected from methylvinylether, ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether,
(ⅳ) vinyl-acetic ester;
(ⅴ) vinylbenzene and
(ⅵ) indenes,
(C) be selected from the presence of the rubbery polymer of conjugated diene monomer of divinyl and isoprene 0-40 part (weight), also can add the comonomer that is selected from vinylbenzene, nitrile and ester, the structural formula of described nitrile monomer is:
Wherein, the R definition is the same, and the structural formula of described ester is:
Wherein, R
1And R
2Definition is the same; Described rubbery polymer contains 50-100%(weight) conjugated diene polymerized and 0-50%(weight) comonomer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US91900992A | 1992-07-23 | 1992-07-23 | |
| US919,009 | 1992-07-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1081690A true CN1081690A (en) | 1994-02-09 |
Family
ID=25441337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93108113 Pending CN1081690A (en) | 1992-07-23 | 1993-07-05 | Improved the polyolefine of barrier propterty |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0586066A3 (en) |
| JP (1) | JPH06157837A (en) |
| CN (1) | CN1081690A (en) |
| TW (1) | TW224982B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1154219A (en) * | 1979-03-15 | 1983-09-27 | Wayne T. Wiggins | Tie layer for co-extruded acrylonitrile copolymers |
| US5084352A (en) * | 1989-11-15 | 1992-01-28 | The Standard Oil Company | Multilayered barrier structures for packaging |
-
1993
- 1993-06-11 TW TW82104647A patent/TW224982B/zh active
- 1993-07-05 CN CN 93108113 patent/CN1081690A/en active Pending
- 1993-07-16 EP EP93305600A patent/EP0586066A3/en not_active Withdrawn
- 1993-07-21 JP JP18023293A patent/JPH06157837A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| TW224982B (en) | 1994-06-11 |
| JPH06157837A (en) | 1994-06-07 |
| EP0586066A2 (en) | 1994-03-09 |
| EP0586066A3 (en) | 1995-08-02 |
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